MIAO Yulu,YANG Peida,SHANG Xuehang,et al.Study on catalytic performance of palladium bismuth two-component catalyst for oxidative esterification of ethylene glycol to methyl glycolate[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(11):29-35.
MIAO Yulu,YANG Peida,SHANG Xuehang,et al.Study on catalytic performance of palladium bismuth two-component catalyst for oxidative esterification of ethylene glycol to methyl glycolate[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(11):29-35. DOI: 10.12434/j.issn.2097-2547.20240464.
Study on catalytic performance of palladium bismuth two-component catalyst for oxidative esterification of ethylene glycol to methyl glycolate
The preparation of methyl glycolate from ethylene glycol as raw material by oxidative esterification is an effective way to realize high value
low carbonization and diversified utilization of ethylene glycol. Nano-gold catalyst is a kind of commonly used catalysts for oxidative esterification
but its application in the reaction is limited due to its poor activity
large amount of precious metals used and high cost. Therefore
it is necessary to develop an efficient and relatively inexpensive catalyst. A series of palladium-based catalysts were prepared by equal volume impregnation method
and their catalytic performance for oxidative esterification of ethylene glycol to methyl glycolate was investigated. It is found that the catalyst activity and product selectivity can be significantly improved by introducing the second component into the palladium-based catalyst. The catalysts were characterized by XRD
TEM
XPS and H
2
-TPR. The results show that the second component forms intermetallic compounds with palladium
resulting in significant changes in the electronic properties of palladium
thereby improving catalyst activity and product selectivity. The types and contents of the second component
the reduction temperature of catalyst
the rati
o of raw materials and the reaction temperature were investigated. It is found that the catalyst introducing bismuth has the best catalytic performance. Under the catalysis of Pd-Bi/Al
2
O
3
catalyst with palladium and bismuth mass fractions of 1.00%
respectively and reduction temperature of 300 ℃
when
n
(ethylene glycol)/
n
(Na
2
CO
3
) = 200 and
n
(methanol)/
n
(ethylene glycol) = 20
the ethylene glycol conversion rate reaches 88.0% and methyl glycolate selectivity reaches 90.1% (120 ℃
KONG L X . Study on the modification and deactivation mechanism of Cu-based catalyst for hydrogenation of methyl glycolate [D ] . Tianjin : Tianjin University , 2020 .
ZHOU J F , DUAN X P , YE L M , et al . Enhanced chemoselective hydrogenation of dimethyl oxalate to methyl glycolate over bimetallic Ag-Ni/SBA-15 catalysts [J ] . Applied Catalysis A: General , 2015 , 505 : 344 - 353 .
LI X X , ZHU Y A , ZHOU J H , et al . Insights into the reaction mechanism of dimethyl oxalate hydrogenation to methyl glycolate over Ag and Cu catalysts [J ] . Natural Gas Chemical Industry , 2018 , 43 ( 6 ): 17 - 23 .
TANG S P , GAO Z M , LUO Z H . Optimization on conditions for the hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Shanghai Chemical Industry , 2018 , 43 ( 4 ): 20 - 23 .
YANG S B , CHIEN I L . Rigorous design and optimization of methyl glycolate production process through reactive distillation combined with a middle dividing-wall column [J ] . Industrial & Engineering Chemistry Research , 2019 , 58 ( 13 ): 5087 - 5348 .
XIAO T T , YANG Z B , ZHEN Z H , et al . Efficient descriptor for designing high-performance Cu-based catalysts for the hydrogenation of dimethyl oxalate to methyl glycolate [J ] . The Journal of Physical Chemistry C , 2024 , 128 ( 19 ): 7926 - 7935 .
ZHANG S G , CUI Y , LIU L L , et al . Preparation of Ag-Ni/KCC-1 and its catalytic performance in the hydrogenation of dimethyl oxalate to methyl glycolate [J ] . Journal of Chemical Engineering of Chinese Universities , 2024 , 38 ( 1 ): 90 - 98 .
LI X Z , BAI F D , ZHANG L , et al . Research and application progress on synthesis process of methyl glycolate [J ] . Low-Carbon Chemistry and Chemical Engineering , 2024 , 49 ( 1 ): 60 - 69 .
颜乐 . 一步法制备乙醇酸甲酯的反应研究 [D ] . 上海 : 华东理工大学 , 2011 .
YAN L . Study on the preparation of methyl glycolate in one step [D ] . Shanghai : East China University of Science and Technology , 2011 .
WANG C , WU C S , XING L X , et al . Facet-dependent long-term stability of gold aerogels toward ethylene glycol oxidation reaction [J ] . ACS Applied Materials & Interfaces , 2020 , 12 ( 35 ): 39033 - 39042 .
LIN L S , BABA H . Method for producing diol derivatives : 1668571A [P ] . 2005-09-14 .
MENG X Z , BAI Y , XU H Y , et al . Selective oxidation of monoethanolamine to glycine over supported gold catalysts: The influence of support and the promoting effect of polyvinyl alcohol [J ] . Molecular Catalysis , 2019 , 469 : 131 - 143 .
HAYASHI T , INAGAKI T , ITAYAMAN , et al . Selective oxidation of alcohol over supported gold catalysts: Methyl glycolate formation from ethylene glycol and methanol [J ] . Catalysis Today , 2006 , 117 ( 1/2/3 ): 210 - 213 .
韩翔 . 乙醇酸甲酯的合成与分离 [D ] . 上海 : 华东理工大学 , 2012 .
HAN X . The synthesis and purification of methyl glycolate [D ] . Shanghai : East China University of Science and Technology , 2012 .
QIN X X . Size effect and carrier effect of Au catalyzed ethylene glycol oxidation esterification [D ] . Shaanxi : Shaanxi Normal University , 2012 .
WANG B H , RAN W L , SUN W J , et al . Direct oxidative esterification of aldehyde with alcohol to ester over Pd/styrene-divinyl benzene copolymer catalyst [J ] . Industrial & Engineering Chemistry Research , 2012 , 51 ( 10 ): 3932 - 3938 .
LIU H X , QIN Q Y , ZHU J , et al . Crystal facet structure dependence and promising Pd-based catalytic materials for resistance toward deactivation and catalytic performance in direct oxidative esterification [J ] . ACS Applied Materials & Interfaces , 2022 , 14 ( 7 ): 9763 - 9780 .
WANG B H , SUN W J , ZHU J , et al . Pd-Pb/SDB bimetallic catalysts for the direct oxidative esterification of methacrolein to methyl methacrylate [J ] . Industrial & Engineering Chemistry Research , 2012 , 51 ( 46 ): 15004 - 15010 .
HOU N , YANG Y . Rapid synthesis of monodisperse porous Pd nanospheres [J ] . Liaoning Chemical Industry , 2024 , 53 ( 6 ): 931 - 934 .
ZHANG W Q , ZHANG X B , WANG J Y , et al . Bismuth-modulated surface structural evolution of Pd 3 Bi intermetallic alloy catalysts for selective propane dehydrogenation and acetylene semihydrogenation [J ] . ACS Catalysis , 2022 , 12 ( 17 ): 10531 - 10545 .
KANG H Q , WU J Z , LOU B H , et al . Controllable deposition of Bi onto Pd for selective hydrogenation of acetylene [J ] . Molecules , 2023 , 28 ( 5 ): 2335 .
LI B B , MA H Y , WANG G C . Acetylene semihydrogenation over Pd-Bi intermetallic compounds: A DFT combined with microkinetic modeling study [J ] . Langmuir , 2024 , 40 ( 36 ): 19043 - 19050 .